JPS60135430A - Production of polyamic acid - Google Patents

Abstract

PURPOSE:To produce a polyamic acid of good heat stability, by reacting a specified dianhydride with a diamine or a diisocyanate and, if desired, oxidizing the product. CONSTITUTION:A dianhydride of formula I (wherein X is S, SO2, -S-R-S-, or -SO2-R-SO2-, and R is a lower alkylene) is reacted with a diamine (e.g., phenyldiamine) or a diisocyanate by heating to 200-250 deg.C at a molar ratio of 0.8- 1.2:1, or a dianyhydride of formula II (wherein X' is S or -S-R-S) is reacted with a diamine or a diisocyanate. The obtained thiourea bond-containing polyamic acid is oxidized with 2-3 equivalent of an oxidizing agent (e.g., H2O2) per mol of the thiourea bonds, and then reduced with an excess of a reducing agent to obtain a polyamic acid.

Description

[Detailed description of the invention] The present invention relates to a novel method for producing polyamic acid.

More specifically, it is possible to produce a polyimide polymer having good thermal stability particularly in the temperature range of 300 to 500°C, and the imidization reaction to the imide polymer can be carried out at a relatively low temperature. This invention relates to a method for producing polyamic acid.

It is well known that aromatic polyimides with excellent heat resistance can be obtained by polycondensing aromatic tetracarboxylic acid anhydrides or derivatives thereof with aromatic diamines or derivatives thereof. This aromatic polyimide is produced by first synthesizing polyamic acid.

It is then cured at high temperature to imidize. For example, aromatic polyamide made from pyromellitic anhydride and diaminodiphenyl ether is the most typical one, but in order to imidize conventional aromatic polyamic acid, it is necessary to cure it at a high temperature of 300° C. or higher.

The present invention solves these problems and further provides a novel polyamic acid capable of producing a polyimide having good thermal stability at 300 to 500°C.

The first invention is.

General formula (11 (in formula 9, X is S, SOx, 8-RS -
or -8Ch RBoz-, where R is a lower alkylene group), and a diamine or diisocyanate.

As the compound represented by general formula (I), 5.5'-
Thiobis (norbonanth 3-dicarboxylic anhydride),
5.5'-methylene dithiobis(norbonane-2.3-
dicarboxylic anhydride), 5.5'-ethylenedithiobis(norbonanth-3-dicarboxylic anhydride), 5.5'
-Propylene dithiobis(norbonane-2,3-dicarboxylic anhydride), 5,5'-sulfonylbis(norbonane-43-dicarboxylic anhydride).

5.5'-Methylenedisulfonylbis(norbonane-2)
．． 3-dicarboxylic anhydride), 5,5'-ethylenedisulfonylbis(norbonane-2,3-cycarphone H
fM hydrate), 5,5'-propylene disulfonyl bis(norponane-43-dicarboxylic acid anhydride), and the like.

These compounds are 5-norbonane-2,3-dicarboxylic anhydride, hydrogen sulfide, and methanedithiol.

It can be obtained by addition reaction of sulfur-containing compounds such as ethanedithiol and propylenedithiol.

Alternatively, by oxidizing the thus obtained compound having a thioether bond with an oxidizing agent.

By converting S to 802, the above general formula (Il, X
A compound containing -802- can be obtained.

In the present invention, the diamine includes:

A phenyldiamine represented by the general formula tm+ or a benzene nucleus-substituted product thereof.

General formula (1’/) Blasphemy.

OOCH3 Fs words Fs and aromatic diamines of these substituents, and further.

There are aliphatic or cycloaliphatic diamines. From the viewpoint of heat resistance, it is preferable to use aromatic diamines.

Aromatic diamines include 2,2-bis(4-(4-aminophenoxy)phenyl)propane, λ2-bis[3
-Methyl-4-(4-aminophenoxy)phenyl]furopane, 2,2-bis[3-chloro-4-(4-aminophenoxy)phenyl]propane, 2-bis[3-bromo-4-(4 -aminophenoxy)phenyl]propane, 2.2-bis[3-ethyl-4-(4-aminophenoxy)phenyl]propane, 2.2-bis[: 3-
Furopyru-4-(4-aminophenoxy)phenyl]
Propane, 2,2-bis[3-inopropyl-4-(4
-aminophenoxy)phenyl]propane, 2,2-bis[3-butyl-4-(4-aminophenoxy)phenyl]propy, 2,2-bis[3-Sec-butyl]
- (4-aminophenoxy)phenyl]propane, 2
12-bis[3-methoxy-4-(4-aminophenoxy)phenyl]propane.

2.2-bis[3-ethoxy-4-(4-aminophenoxy)phenyl]furopane, 2-bis(3゜5-dimethyl-4-(4-aminophenoxy)phenyl)furopane, 2.2-bis (3,5-cyclo4-(4-aminophenoxy)phenyl)propane, 2,2-bis[
3,5-dibromo-4-(4-aminophenoxy)phenyl]globan, 2,2-bis[3,5-dimethoxy-
4-(4-aminophenoxy)phenyl]furopane, 2
．． 2-bis[3-chloro-4-(4-aminophenoxy)-5-methylphenyl]furopane, 1,1-bis[:
4-(4-aminophenoxy)phenyl]ethane, 1.
1-bis[3-methyl-4-(4-aminophenoxy)
phenyl]ethane, 1,1-bis(3-1'rolo-4-
(4-Aminophenoxy)phenyl]ethane.

1.1-bis[3-promo4-(4-aminophenoxy)phenyl]ethane, l,1-bis[3-ethyl-4
-(4-aminophenoxy)phenyl]ethane, 1,1
-bis[3-propyl-4-(4-aminophenoxy)
phenyl]ethane, 1,1-bis[3-improvil-
4-(4-aminophenoxy)phenyl]ethane, 1.
1-bis(3-butyl-4-(4-aminophenoxy)
phenyl]ethane/, 1.1-bis(3-see-butyl-4-(4-aminophenoxy)phenyl)ethane, 1
．． 1-bis[3-methoxy-4-(4-aminophenoxy)phenyl]ethane, 1.1-bis[3-ethoxy-
4-(4-aminophenoxy)phenyl]ethane, 1.
1-bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis(3,5-dichloro-4-(4-aminophenoxy)phenyl)ethane, 1.l- Bis[3,5-dibromo-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3,5
-dimethoxy-4-(4-aminophenoxy)phenyl]ethane, 1°1-bis[3-chloro-4-(4-aminophenoxy)phenyl-5-methylphenyl]ethane.

Bis[4-(4-aminophenoxy)phenylcomethane, bis[3-methyl-4-(4-aminophenoxy)phenylcomethane, bis[3-chloro-4-(4-aminophenoxy)phenylcomethane, Bis [3-promo 4
-(4-aminophenoxy)phenylcomethane, bis[
3-Ethyl-4-(4-aminophenoxy)phenylcomethane.

Bis[3-propyl-4-(4-aminophenoxy)phenylcomethane, bis[3-improvyl-4-(4-
aminophenoxy) phenylcomethane, bis[3-butyl-4-(4-aminophenoxy)phenylcomethane,
Bis[: 3-5ee-butyl-4-(4-aminophenoxy)phenylcomethane, bis[3-methoxy-4-
(4-aminophenoxy)phenylcomethane, bis[3
-ethoxy-4-(4-aminophenoxy)phenylcomethane, bis[3,5-dimethyl-4-(4-aminophenoxy)phenylcomethane, bis[: 3,5-dichloro-4-(4-amino phenoxy)phenylcomethane, bis[3,5-dibromo-4-(4-aminophenoxy)phenylcomethane, bis(3,5-dimethoxy-4
-(4-aminophenoxy)phenylcomethane, bis[
3-chloro-4-(4-aminophenoxy)-5-methylphenylcomethane.

1, 1.1. 3,3-hexafluoro-2,2-bis[4-(4-aminophenoxy)phenyl]propane.

i, 1.1.3.3.3-hexachloro-42-bis[4-(4-aminophenoxy)phenyl]propane.

3.3-bisC4-<4-aminophenoxy)phenyl]pentane, 1,1-bis(4-(4-aminophenoxy)phenyl)propane, 1,1,1,3,3.3-
Hexasulfolose 2-bis-(3,5-dimethyl-4
-(4-aminophenoxy)phenyl]propane, 1
．． 1.1.3.3.3-hexachloro-2,2-bis(
3,5-dimethyl-4-(4-aminophenoxy)phenyl]propane, 315-bis(3,5-dimethyl-4
-(4-aminophenoxy)phenyl]pentane, 1.
1-bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]propane, t, i.

1,3.3.3-hexafluororo2.2-bis[3
,5-dibromo-4(4-aminophenoxy)phenyl]propane, 1.1.1.3.3.3-hexachloro-42-bis[3,5-dibromo-4-(4-aminophenoxy)phenyl ] Propane, 3.3-bis (3゜5
-dibromo-4-(4-aminophenoxy)phenyl]
Pentane, 1,1-bis(:3,5-dibromo-4-(
4-aminophenoxy)phenyl]propane, 2.2-
Bis(4-(4-aminophenoxy)phenylcobutane, 2.2-his(3-methy#-4-(4-aminophenoxy)phenylcobutane).

2.2-bis[3,5-dimethyl-4-(4-aminophenoxy)phenylcobutane, 22-bis[tortoise 5-dibromo-4-(4-aminophenoxy)phenylcobutane, i, i, t , a, turtle a-hexafluoro-sufu-bis[3-methyl-4-(4-aminophenoxy)phenyl]furopane, m-7 enylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4
．． 4'-diaminodiphenyl ether, 4.4'-diaminodiphenyl sulfone.

4.4'-diaminodiphenylpropane-2,2,4,
4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 4,4'-diaminodiphenylethane.

m-tolylenediamine, p-tolylenediamine, 3
．． 4'-Diaminobenzanilide, 1.4-diaminonaphthalene, 3.3'-dichloro-4,4'-diaminodiphenyl, benzidine+, 4.4'-diaminodiphenylamine, 4.4'-') aminodiphenyl- N-methylamine, 4.4'-diaminodiphenyl-N-phenylamine, 3.3'-diaminodiphenylsulfone,
44'-Diaminodiphenyldiethylsilane.

Examples include 44'-diaminodiphenylsilane, and examples of aliphatic or cycloaliphatic diamines include piperazine.

Hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, p-xylylene diamine, m-xylylene diamine, tetramethylene diamine, dodecamethylene diamine, 4,4-dimethylhebutamethylene diamine, 3-Methylhebutamethylenediamine, 2.11-diaminododecane.

1, 1,2-diaminooctadecane, cyclohexane 1
．． 3-diamine, cyclohexane 1,4-diamine, etc.

Examples of diisocyanates include those obtained by replacing the amine group of the above diamine with an incyanate group.

In the present invention, the reaction between the diacid anhydride represented by the general formula [11] and the diamine or diisocyanate is performed using a non-containing compound such as dimethylacetamide, dimethylsulfoxide, dimethylformamide, N-methylpyrrolidone, hexamethylphosphoric triamide, etc. In a protic polar solvent, preferably from room temperature to 150°C, particularly preferably from 60 to 80°C.
It is carried out at a temperature of

The diacid anhydride and diamine or diisocyanate represented by the general formula (11) have a ratio of the former/latter of 0.8/1 to 1
．． It is preferable to use them in a ratio of 2/1 (molar ratio), particularly preferably in about equimolar amounts.

The polyamic acid obtained by the present invention can undergo an imidization reaction by heating to a relatively low temperature (for example, 200 to 250°C) to produce a polyimide polymer.

At this time, polyamic acid is in the form of a lump or film.

It can be in any form such as a solution. When in solution form, it may be carried out in the above-mentioned polar organic solvent.

The second invention is.

A dianhydride represented by the general formula (nl (wherein 1 X' is S or -8-R-8-, and R is a lower alkylene group) and a diamine or diisocyanate are reacted. The present invention relates to a method for producing a polyamic acid, which comprises obtaining a polyamic acid having a thioether bond and then oxidizing it.

In the second invention, the steps up to the production of polyamic acid having a thioether bond are different from those in the first invention except for using a compound represented by the general formula (nl) among the diacid anhydrides represented by the general formula (1). In the second invention, sulfur is converted to SO! by oxidizing the thus obtained polyamic acid having a thioether bond.
A polyamic acid converted to can be obtained.

The oxidation reaction can be carried out using an oxidizing agent. The oxidizing agent is preferably used in an amount of 2 to 1 mole of thioether bond.
3 equivalents are used. The amount of oxidizing agent may be less than 1 equivalent relative to the thioether bond.

At this time, part of the sulfur is converted to BO2.

The oxidation reaction can be carried out in the polar organic solvents mentioned above, and the reaction temperature is between about 0° C. and the boiling point of the solvent. Preferably, an acid such as acetic acid is present in the reaction system.

Oxidizing agents include hydrogen peroxide, potassium permanganate,
Peroxides such as benzoyl peroxide and di-tert-butyl peroxide, and organic peracids such as peracetic acid, perbenzoic acid and monoperphthalic acid can be used.

After the reaction is completed, excess oxidizing agent may be reduced with a reducing agent such as sodium bisulfite. In addition, if the carboxyl group of polyamic acid is oxidized, reduce it with a reducing agent in the same way,
Can be converted back to carboxyl group.

Next, examples of the present invention will be shown.

Example 1 l-A) Synthesis of dicarboxylic anhydride: 5,5'-ethylenedithiobis(norbonane-2.3) from 5-norbonane-2,3-dicarboxylic anhydride (hereinafter abbreviated as HAC) and ethanedithiol - dicarboxylic acid anhydride) (hereinafter referred to as
Synthesis of ETNA).

5-norbonane-2,3-dicarboxylic anhydride 19.7
9 (0.12ml with oil seal thermometer.

It was placed in a 300c♂ four-loop flask equipped with a reflux tube and a three-one motor, and nitrogen was passed through it. 9. Add ethanedithiol using a syringe through the serum cap while passing nitrogen.
6 cm” (0.06 mol) was injected.

The temperature was maintained at 100° C. with a mantle heater, and the reaction was allowed to proceed for 3 hours while stirring with a three-one motor.

At this time, 5-norbonane-2,3-dicarboxylic anhydride was dissolved in ethanedithiol and became a transparent homogeneous liquid, but as the reaction progressed, a white substance precipitated and the liquid became non-uniform again. After cooling to room temperature.

50 cm" of ethyl acetate was added and allowed to stand overnight. Next, an additional 200 C1+" of ethyl acetate was added and filtered through a 04 glass filter. Then ethyl acetate 200
Washing was repeated 3 times using "an".The yield was 45
．． 6n, the melting point of the produced monomer was 252°C. The reaction formula is shown below.

(HAC) (ETNA) The structure of the synthesized ETNA was confirmed using a chemical method and a NM method. In addition, to confirm the introduction of sulfur, a small piece of sodium was placed in a small test tube in a fume hood, 0.1 g of monomer was added, the bottom was heated with a flame, the bottom was crushed in 20 cc of purified water, and the solid was thoroughly ground and extracted. After that, I went through the process. Sodium nitroprusside solution in P liquid ice
Add ~2 drops.

I checked to see if it turned reddish-purple. As a result of NM analysis, no double bond peak was clearly observed, and bromine/
Since the result of detection of unsaturated bonds using carbon tetrachloride was negative, it was confirmed that thiol was added to the double bond portion. Also, IR, analysis results, 1860cm-',
A large peak believed to be that of acid anhydride was observed at 17.80 cm-', but no peak of carboxylic acid was observed, indicating that no ring opening occurred during one reaction. In addition, the introduction of sulfur was confirmed from the fact that it turned reddish-purple with a sodium nitroprusside solution.

1-B) Synthesis of polyamic acid (ETNA-1) (hereinafter referred to as APE) from ETNA and 4,4'-diaminodiphenyl ether (hereinafter referred to as DAPE) 50c equipped with a stirrer, nitrogen introduction tube, reflux tube, and drying tube. Nitrogen was passed through the Mitsuro flask to make the inside of the flask anhydrous. 4.
4'-diaminodiphenyl ether 0.89 (0,0
04 mol) was placed in a flask, and 10 i of dimethylacetamide (hereinafter abbreviated as DM Ac) was added as a solvent to dissolve it.

Keep it at 60℃ using a mantle heater.
-Ethylene dithiobis(norbonane-2.3=dicarboxylic acid anhydride) 1.689 (0,004 m0l) was added and washed into the flask using 6 cm3 of DMAc.

The reaction mixture was kept at 60°C and stirred with a stirrer for 2 hours.
After reacting for an hour, the mixture was allowed to cool to room temperature. Thereafter, the reaction solution was poured into 1000 cm" of purified water and reprecipitated. After drying, the solution was dissolved in 20 cm" of DMAc again, poured into purified water, and reprecipitated twice for purification. The yield was 98% or more, and the polymer was obtained almost quantitatively.

The reaction formula is shown below.

Synthesis was carried out in the same manner as ETNA and DAPE using dimethylformamide (DMF) and hexamethylphosphoric triamide (HMPA) as solvents.

Table 1 shows the properties of the obtained polymer. Also.

The obtained polymer was heated, and the temperature at which imidization started and the decomposition temperature (Ta) of the obtained polyimide polymer were measured using a differential scanning calorimeter (BSC). The results are shown in Table 1. Furthermore, the reduced viscosity of the obtained polyamic acid (concentration 0.1 g/10 dl DMA c.

(measured at 30°C) and acid values are shown in Table 1.

Example 2 ETNA of Example 1 1.689 (0,004m0d
) and 2,2-bis(:4-(4-aminophenoxydiphenylpropane)] (hereinafter abbreviated as DAPP) 1.649
(0,04moA') to polyamic acid (hereinafter ETNA)
-DAPP) was synthesized in the same manner as in Example 1.

The reaction formula is shown below.

ETNA+1) APP-1 A mixed solvent of equal weights of DMAc, N-methylpyrrolidone (NMP) and HMPA was used as a reaction solvent.

A polyamic acid was obtained in the same manner as above using a mixed solvent of NMP/HMPA=2/1 (weight ratio).

The imidization initiation temperature of these polyamic acids, the decomposition temperature of polyimide, and the reduced viscosity and acid value of the polyamic acids are shown first.

Example 3 ETNA from Example 1 1.68 g (0,004 mo
p-phenylenediamine (hereinafter abbreviated as PDA) 0
．． 8g (0,004mol polyamic acid (hereinafter E)
(abbreviated as TNA-PDA) was synthesized in the same manner as in Example 1. The reaction formula is shown below.

Table 1 shows the imidization start temperature of the obtained polyamic acid, the decomposition temperature of the obtained polyimide, and the reduced viscosity and acid value of the polyamic acid.

Example 4 4-A) 5,5'-thiobis(
norbonane-2,3-dicarboxylic anhydride) (hereinafter referred to as TN
Synthesis of abbreviation A.

Put 32.8 g of 5-norbonane-2,3-dicarboxylic anhydride into a fourth 500 am3 flask equipped with a three-one motor, reflux tube, thermometer, and capillary.
It was dissolved in 100 cm3 of dry benzene.

Nitrogen was passed through the capillary to replace the inside of the flask with nitrogen, and then 9 minutes of AIBN 1.19 was added. Next, the temperature of the oil bath was raised to 80° C. while vigorously blowing hydrogen sulfide through the capillary.

When stirring was continued with a three-one motor while maintaining the temperature of the oil bath at 80° C., what was initially a transparent and uniform solution began to precipitate white crystals at about 40 minutes t1. about 7
When the 0 minute diameter solution became mushy, heating was stopped and the solution was allowed to cool to room temperature. Then add 100 c♂ of benzene and
Benzene 100% after being removed using a 4-glass filter
The operation of washing with CII+3 was repeated twice.

After drying, it was purified by recrystallization using dioxane.

The reaction formula is shown below.

The obtained 7-mer was converted to KMn in the same manner as in Example 1.

The structure was confirmed by sulfur analysis.

4-B) Polyamic acid from TNA and DAPE (hereinafter referred to as T
Synthesis of NA-DAPE) Nitrogen was passed through a 50cII+'' three-way flask equipped with a stirrer, a nitrogen guide tube, and a thermometer to make the flask anhydrous. 20
5,5'-thiobis(norbonane-2.3-
dicarboxylic acid anhydride) was added.

Polymerization was then carried out by stirring for 2 hours while maintaining the temperature at 60°C.

Thereafter, it was allowed to cool to room temperature, and the 9 reaction solution was poured into 1000 an" of purified water for reprecipitation. After drying, reprecipitation purification was further performed twice using DMAc.

In addition, NMP/HMPA (1:1) was added to the solvent in the same manner.
Polymerization was carried out using the mixed solution.

The reaction formula is shown below.

TNA+DAPE−÷ Table 1 shows the imidization start temperature of the obtained polyamic acid, the decomposition temperature of the obtained polyimide, and the reduced viscosity and acid value of the polyamic acid.

Example 5 Nanatsuma-TNA obtained in Example 4 1.829 (0,00
5mo/) and DAPDZo 5g (0,005mo
Polyamic acid (hereinafter abbreviated as TNA-DAPP) was synthesized in the same manner as in Example 4 using the solvent DMAc.

The reaction formula is shown below.

TNA-)-DAPP-1 Table 1 shows the imidization initiation temperature of the obtained polyamic acid, the decomposition temperature of the obtained polyimide, and the reduced viscosity and acid value of the polyamic acid.

Example 6 F! of Example 2! The TNA-DAPP polymer was sulfonated in the following manner.

Polymer ETNA-DAPP1.5 synthesized in Example 2
Put g into a 200cm Mitsuro flask and D M A
Add 3 ml of c20 and dissolve.

Next, 20 cm” of acetic acid was added to this solution.
1.3 g of well-ground n04 was gradually added and stirred vigorously for 2 hours.

Thereafter, about 100 an'' of purified water was added to the reaction solution.

A small amount of sulfuric acid was added and sodium bisulfite was added until the color of KMnO4 disappeared. Since a substance other than the reaction product was soluble in water, it was filtered using a 04 glass filter to obtain a pale yellow substance.

The reaction formula is shown below. Sulfonated ETNA-DAP
P polymer is abbreviated as 8ETNA-DAPP.

The imidization initiation temperature of the obtained polyamic acid, the decomposition temperature of the obtained polyimide, and the reduced viscosity and acid value of the polyamic acid are shown in Table 1.

Comparative Example 1 Polymer from pyromellitic anhydride and 4,4'-diaminodiphenyl ether (DAPE) (abbreviated as I'PA)
50 with a synthesis stirrer, nitrogen introduction tube, thermometer, and reflux tube.
Pass nitrogen through a cm3 Mitsuro flask and
Diaminodiphenyl ether 1.09 (0,005 mo
16 cm3 of DMAc was added and dissolved.

Add to this pyromellitic anhydride to 9 g (o, oo 5 mol)
) was added. At this time, 9 fevers were observed. 3 more e
When the mixture was washed with 11" of DMAc and stirred at room temperature for 20 minutes, the viscosity increased and the sister stirrer no longer rotated.Additionally 20 cm" of DMAc was added to the reaction solution and the mixture was stirred for 20 minutes at room temperature.
It was poured into the purified water of step d and reprecipitated.

Thereafter, reprecipitation purification was repeated twice. The reaction formula is shown below.

Polyamide Polyimide Table 1 shows the imidization start temperature, reduced viscosity and acid value of the polyamic acid obtained.

According to the present invention, a novel polyamic acid can be produced, and the polyamic acid can be imidized at a relatively low temperature.

Claims (1)

[Claims] 1. General formula (11 (in formula 9, X is 8.802.8 RS- or -8Ch R-80z-, where R is a lower alkylene group) A method for producing a polyamic acid, characterized by reacting a diacid anhydride represented by the above formula with a diamine or diincyanate.
-, where 几 is a lower alkylene group) and a diamine or diisocyanate are reacted to obtain a polyamic acid having a thioether bond, which is then oxidized. Manufacturing method-